A thorough reinvestigation of the hydroboration–oxidation of methylene epoxycyclohexane 3 has revealed the formation of a direct precursor of the hitherto unreported 5-epi-cyclophellitol. Hydroboration of the starting precursor 3 takes place with total and opposite stereocontrol to that previously described in the literature. The stereochemistry of this new cyclophellitol isomer has been unambiguously confirmed by comparison with reference compounds obtained by independent methods.